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An NMR and Quantum Mechanical Investigation of Solvent Effects on Conformational Equilibria of Butanedinitrile

Kent, David R., IV and Dey, Neelendu and Davidson, Fredric and Gregoire, Françoise and Petterson, Krag A. and Goddard, William A., III and Roberts, John D. (2002) An NMR and Quantum Mechanical Investigation of Solvent Effects on Conformational Equilibria of Butanedinitrile. Journal of the American Chemical Society, 124 (31). pp. 9318-9322. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20151001-101403030

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Abstract

Vicinal proton−proton NMR couplings and ab initio quantum mechanics have been used to investigate solvent effects on conformational equilibria of butanedinitrile. The trans and gauche conformations are about equally favored at room temperature in solvents of low dielectric constant while the equilibrium is essentially the statistical proportions of one-third trans and two-thirds gauche in water with a high dielectric constant. The coupling assignments were confirmed with the aid of stereospecific deuterium-labeled (R,R or S,S)-1,2-dideuteriobutanedinitrile. The calculations support the observed trends. Similar results were observed for 1,2-dibromo- and dichloroethanes.


Item Type:Article
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http://dx.doi.org/10.1021/ja020535nDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja020535nPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja020535nRelated ItemSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2002 American Chemical Society. Received April 12, 2002. Publication Date (Web): July 10, 2002. We thank the donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this research. We are also deeply indebted to the Summer Undergraduate Research Fellowship Program (SURF), the Beckman Institute of the California Institute of Technology, the E. I. Du Pont Co., and Dr. & Mrs. Chester M. McCloskey for their helpful financial assistance. D.R.K. is grateful for support of part of this research by a graduate fellowship from the Fannie and John Hertz Foundation. The quantum chemistry calculations reported here were funded by DOE-BCTR (DEFG36-93CH105 81, David Boron). The facilities of the MSC are also supported by grants from NSF (CHE 95-22179 and ASC 92-100368), Chevron Petroleum Technology Co., Saudi Aramco, Asahi Chemical, Owens-Corning, Exxon, Chevron Chemical Co., Chevron Research and Technology Co., Avery-Dennison, Hercules, BP Chemical, and the Beckman Institute.
Funders:
Funding AgencyGrant Number
American Chemical Society Petroleum Research FundUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
E. I. Du Pont Co.UNSPECIFIED
Dr. & Mrs. Chester M. McCloskeyUNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Department of Energy (DOE)DE-FG36-93CH10581
NSFCHE 95-22179
NSFASC 92-100368
Chevron Petroleum Technology Co.UNSPECIFIED
Chevron Research and Technology Co.UNSPECIFIED
Avery-DennisonUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
HerculesUNSPECIFIED
BP ChemicalUNSPECIFIED
Record Number:CaltechAUTHORS:20151001-101403030
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151001-101403030
Official Citation:An NMR and Quantum Mechanical Investigation of Solvent Effects on Conformational Equilibria of Butanedinitrile David R. Kent, IV, Neelendu Dey, Fredric Davidson, Françoise Gregoire, Krag A. Petterson, William A. Goddard, III, and John D. Roberts Journal of the American Chemical Society 2002 124 (31), 9318-9322 DOI: 10.1021/ja020535n
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60653
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:02 Oct 2015 16:15
Last Modified:02 Oct 2015 16:15

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